Comparative study of different approaches of multicrystalline silicon texturing for solar cell fabrication

Alkali etchant cannot produce uniformly textured surface to generate satisfactory open circuit voltage as well as the efficiency of the multi-crystalline silicon (mc-Si) solar cell due to the unavoidable grain boundary delineation with higher steps formed between successive grains of different orientations during alkali etching of mc-Si. Acid textured surface formed by using chemicals with HNO₃–HF–CH₃COOH combination generally helps to improve the open circuit voltage but always gives lower short circuit current due to high reflectivity. Texturing mc-Si surface without grain boundary delineation is the present key issue of mc-Si research. We report the isotropic texturing with HF–HNO₃–H₂O solution as an easy and reliable process for mc-Si texturing. Isotropic etching with acidic solution includes the formation of meso- and macro-porous structures on mc-Si that helps to minimize the grain-boundary delineation and also lowers the reflectivity of etched surface. The study of surface morphology and reflectivity of different mc-Si etched surfaces has been discussed in this paper. Using our best chemical recipe, we are able to fabricate mc-Si solar cell of 14% conversion efficiency with PECVD AR coating of silicon nitride film. The isotropic texturing approach can be instrumental to achieve high efficiency in mass production using relatively low-cost silicon wafers as starting material with the proper optimization of the fabrication steps.     

Measurements of effective optical reflectivity using a conventional flatbed scanner—Fast assessment of optical layer properties

A conventional flatbed scanner equipped with an additional diffusor is used for rapid measurements of an important figure of merit for optical surfaces, the effective reflectivity of devices such as solar cells. The application of the technique to multicrystalline silicon wafers with light-trapping structures obtained by electrochemical etching is shown. The use of this method for rapid quality control in production environments as well as in the lab is envisaged: even with a non-optimized diffusor, a spatial resolution of 0.1×0.1 mm² can be achieved, with an accuracy of the reflectivity measurements of 1% and data-acquisition times around 10 s per wafer.     

Deposition pressure effects on material structure and performance of micromorph tandem solar cells

Tandem solar cells represent an elegant way of overcoming the efficiency limits of single-junction solar cells and reducing the light-induced degradation of amorphous silicon films. Stacked structures consisting of an amorphous silicon top cell and a microcrystalline silicon bottom cell allow a good utilization of the solar spectrum due to the band gap values of the two materials. These devices, firstly introduced by the IMT research group, were designated as “micromorph” tandem solar cells. To better exploit this concept, it is important to tune parameters like the band gaps and the short-circuit currents.In this work, we have realized micromorph tandem solar cells on Asahi U-type TCO-covered glass substrates. The intrinsic layer of both the amorphous top cell and the microcrystalline bottom cell is grown by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) at 100 MHz at low substrate temperature (150 °C). Finally, a ZnO reflector and a metal contact complete the structure. No intermediate optical mirror between the two cells is used at this stage. Undiluted a-Si:H, with reduced band gap when compared to H₂-diluted amorphous silicon, is used as absorber layer in the top cell. As for the bottom cell, the high-pressure–high-power regime (up to 267 Pa–80 W) has been explored aiming at growing high-quality microcrystalline silicon at large deposition rates. The effect of the structural composition of the microcrystalline absorber layer on the current–voltage characteristic and spectral response of tandem devices has been investigated. An efficiency of 11.3% has been obtained with short-circuit current densities around 13 mA/cm², open-circuit voltages 1.34 V and fill factors 66%.     

Texturing of large area multi-crystalline silicon wafers through different chemical approaches for solar cell fabrication

Surface texturing of silicon can reduce the reflectance of incident light and hence increase the conversion efficiency of solar cells. Comparatively lesser concentrated (10%) standard alkaline (NaOH/KOH) solution does not give good textured multi-crystalline silicon (mc-Si) surface, which could give satisfactory open-circuit voltage. This is due to grain-boundary delineation with steps formed between successive grains of different orientations. In this work an attempt has been made to obtain a well-textured mc-Si surface through three different approaches. The first two are with two different types of acid solutions and the third with concentrated alkaline NaOH. Solutions of HF–HNO₃–CH₃COOH/H₂O system with different concentrations of HF and HNO₃ were used for texturing. The results on the effect of texturing of these three solutions on the surface morphology of very large area (125 mm×125 mm) mc-Si wafer as well as on the performance parameters of solar cell are presented in this paper. Attempts have been made to study extensively the surface morphologies of mc-Si wafers in two effective regions of the isoetch curves of the HF:HNO₃:diluent's system. Also we studied the reflectance, uniformity, spectral response, short-circuit current, open-circuit voltage, fill factor and dark current–voltage of the cells fabricated using wafers textured with the three different methods. Short-circuit current of the solar cells fabricated using acid-textured wafers were measured to be in the range of 4.93 A. This value is 0.37 and 0.14 A higher than the short-circuit current values measured in the cells fabricated with isotextured and alkaline-textured wafers, respectively.     

Optimisation of NaOH texturisation process of silicon wafers for heterojunction solar-cells applications

The formation of a pyramidal structure on the surface of 〈1 0 0〉-oriented monocrystalline-silicon wafers is an effective and well known method to reduce reflection losses from the front surface of both silicon solar cells and silicon-heterojunction solar cells (SHJs). The consequence of this texturisation is an important optical gain, with a subsequent increase of the short-circuit current density (J_sc) and thus of the conversion efficiency of the devices. On the other hand, silicon-heterojunction solar cells are critically affected by the surface quality of the c-Si substrates, so the right combination of optimum texturisation- and cleaning steps previous to emitter (a-Si:H) deposition are indispensable in the fabrication process. The main goal of this work has been to perform a systematic and comprehensive analysis aimed at optimising the texturisation process based on the use of alkali solutions of NaOH with de-ionised water (DIW) and isopropyl alcohol (IPA) in different types of monocrystalline-silicon wafers for silicon-heterojunction solar-cell (a-Si:H/c-Si) applications. Three types of 〈1 0 0〉 silicon substrates have been used: polished float-zone (FZ) wafers and rough- (as-cut) and polished Czochralski (CZ) wafers. The texturisation process has been evaluated from images obtained by Scanning Electron Microscopy (SEM) and from hemispherical-reflectance spectra. Different etching times, temperatures and NaOH concentrations of the solutions as well as cleaning treatments of the wafers prior to the texturisation process have been analysed. Results show different conditions of the optimum texturisation process for each type of silicon wafers. An effective texturisation of FZ and CZ substrates has been achieved. Finally, SHJ solar cells have been obtained from FZ and CZ silicon wafers textured by the chemical processes optimised in this work.     

Structural, electrical and photovoltaic characterization of Si nanocrystals embedded SiC matrix and Si nanocrystals/c-Si heterojunction devices

Thin films of Si nanocrystals (Si NCs) embedded in a silicon carbide (SiC) matrix (Si-NC:SiC) were prepared by alternating deposition of Si-rich silicon carbide (Si_1−xC_x) and near-stoichiometric SiC mutilayers (Si_1−xC_x/SiC) using magnetron cosputtering followed by a post-deposition anneal. Transmission electron microscopy and Raman spectroscopy revealed that the Si NCs were clearly established, with sizes in the range of 3–5 nm. Optical studies showed an increase in the optical band gap after annealing from 1.4 eV (as-deposited) to 2.0 eV (annealed at 1100 °C). P-type Si-NC:SiC/n-type crystalline silicon (c-Si) heterojunction (HJ) devices were fabricated and their electrical and photovoltaic properties were characterized. The diode showed a good rectification ratio of 1.0×10⁴ at the bias voltage of ±1.0 V at 298 K. The diode ideality factor and junction built-in potential deduced from current–voltage and capacitance–voltage plots are 1.24 and 0.72 V, respectively. Illuminated I–V properties showed that the 1-sun open-circuit voltage, short-circuit current density and fill factor of a typical HJ solar cell were 463 mV, 19 mA/cm² and 53%, respectively. The external quantum efficiency and internal quantum efficiency showed a higher blue response than that of a conventional c-Si homojunction solar cell. Factors limiting the cell's performance are discussed.     

Texturisation of multicrystalline silicon wafers for solar cells by reactive ion etching through colloidal masks

Texturing of multicrystalline silicon solar cells by reactive ion etching (RIE) is demonstrated as an attractive solution for lowering of reflectance. A suitable sequence of processes is developed to exploit the advantage of RIE in combination with “natural lithography” based on colloidal masks. A homogeneous particle coverage on 4 in. monocrystalline wafers and on 100×100 mm² multicrystalline wafers (Baysix) has been achieved. Finally, texture is obtained by RIE patterning. Data of optical properties are presented. A significant lowering of the reflection of textured wafers compared to untexture is achieved for all states of solar cell production.     

Texturization of multicrystalline silicon wafers for solar cells by chemical treatment using metallic catalyst

A new etching method for texturing multicrystalline p-type Si wafers for solar cells was developed. In this method, we used platinum or silver particles as the catalysts, which were loaded on the wafers by means of the electroless-plating technique. After deposition of the catalysts, the wafers were etched and textured in HF solution, to which in some cases chemical oxidants were added. The solar cells (4 cm²) manufactured from the textured wafers showed efficiency as high as 16.6%, which was about 1% (absolute) higher than that of the cells made from the wafers treated by the conventional alkaline method.     

Novel low-cost approach for removal of surface contamination before texturization of commercial monocrystalline silicon solar cells

This paper reports a novel approach on the surface treatment of monocrystalline silicon solar cells using an inorganic chemical, sodium hypochlorite (NaOCl) that has some remarkable properties. The treatment of contaminated crystalline silicon wafer with hot NaOCl helps the removal of organic contaminants due to its oxidizing properties. The objective of this paper is to establish the effectiveness of this treatment using hot NaOCl solution before the saw damage removal step of the conventional NaOH texturing approach. A comparative study of surface morphology and FTIR analyses of textured monocrystalline silicon surfaces with and without NaOCl pre-treatment is also reported. The process could result in a significant low cost approach viable for cleaning silicon wafers on a mass production scale.     

Ribbon Si solar cells with efficiencies over 18% by hydrogenation of defects

We have fabricated 4 cm² solar cells on String Ribbon Si wafers and edge-defined film-fed grown (EFG) Si wafers with using a combination of laboratory and industrial processes. The highest efficiency on String Ribbon Si wafer is 17.8% with an open circuit voltage (V_oc) of 620 mV, a short circuit current density (J_sc) of 36.8 mA/cm² and a fill factor (FF) of 0.78. The maximum efficiency on EFG Si is 18.2% with a V_oc of 620 mV, a J_sc of 37.5 mA/cm² and a FF of 0.78. These are the most efficient ribbon Si devices made to date, demonstrating the high quality of the processed Si ribbon and its potential for industrial cells. Co-firing of SiN_x and Al by rapid thermal processing was used to boost the minority carrier lifetime of bulk Si from 3–5 μs to 70–100 μs. Photolithography-defined front contacts were used to achieve low shading losses and low contact resistance with a good blue response. The effects of firing temperature and time were studied to understand the trade-off between hydrogen retention and Al-doped back surface field (Al-BSF) formation. Excellent bulk defect hydrogenation and high-quality thick Al-BSF formation was achieved in a very short time (1 s) at firing temperatures of 740–750 °C. It was found that the bulk lifetime decreases at annealing temperatures above 750 °C or annealing time above 1 s due to dissociation of hydrogenated defects.     

The enhancement of homogeneity in the textured structure of silicon crystal by using ultrasonic wave in the caustic etching process

The presence of the ultrasonic wave in the caustic etching process enhances the etching rate and results in a finer, and more homogeneous, textured structure. The silicon solar cell, texture etched for 20 min at 60°C in the caustic solution with ultrasonic wave, gives higher cell performance than the cell texture etched for 40 min at 70°C without ultrasonic wave. This comparison indicates a strong possibility of lowering the texturing cost of the silicon crystal by saving time and expensive chemicals normally employed in the texturisation of the crystalline silicon.     

Study of electrical properties of oxidized porous silicon for back surface passivation of silicon solar cells

Back surface passivation becomes a key issue for the silicon solar cells made with thin wafers. The high surface recombination due to the metal contacts can be lowered by reducing the back contact area and forming local back surface field (LBSF) in conjunction with the passivation with dielectric layer. About 3×10^-7 m thick porous silicon (PS) layer with pore diameter mostly of 1×10^-8–5×10^-8 m was formed by chemical etching of silicon using the acidic solution containing hydrofluoric acid (HF), nitric acid (HNO₃) and De-ionized water in the volume ratio 1:3:5 at 298 K for which etching time was kept constant for 360 s. Electrical properties of oxidized PS was studied through the current–voltage (I–V) and capacitance–voltage (C–V) characteristics of the metal–insulator–semiconductor (MIS) device in which the oxidized PS was used as an insulating layer and the results were further analyzed. The C–V curves of all the studies MIS devices showed the negative flatband voltage varying from -2 to , confirming that the oxidized layer of PS has fixed positive charge.     

Photovoltaic properties of SnS based solar cells

Polycrystalline thin films of tin sulphide have been synthesised using spray pyrolysis. The layers grown at a temperature of 350 °C had the orthorhombic crystal structure with a strong (1 1 1) preferred orientation. The films had resistivities 30 Ω cm with an optical energy band gap (E_g) of 1.32 eV. Heterojunction solar cells were fabricated using sprayed SnS as the absorber layer and indium doped cadmium sulphide as the window layer and the devices were characterised to evaluate the junction properties as well as the solar cell performance. The current transport across the junction has been modelled as a combination of tunnelling and recombination. The best devices had solar conversion efficiencies of 1.3% with a quantum efficiency of 70%.     

An optimized texturing process for silicon solar cell substrates using TMAH

Random pyramidal texturing of silicon solar cell substrates allows to increase the short-circuit current of the device, and it is usually achieved, in commercial solar cells, by chemical anisotropic etching using a potassium hydroxide and isopropyl alcohol solution. Due to some drawbacks of these chemicals, alternative chemical etching solutions are required. Our successful results on the tetramethyl ammonium hydroxide (TMAH), (CH₃)₄NOH, solution for silicon random texturing are reported. Heterojunction solar cells were deposited on textured substrates, indicating the feasibility of TMAH texturing for solar cell fabrication.     

Degradation studies of transparent conducting oxide: a substrate for microcrystalline silicon thin film solar cells

Aluminium doped ZnO films have been developed by RF-magnetron sputtering at 350 °C substrate temperature on glass substrate and commercially available SnO₂-coated glass substrate. The developed ZnO and SnO₂/ZnO films can be used as the substrates of microcrystalline silicon based solar cell. The electrical, optical properties and surface morphologies of ZnO film and SnO₂/ZnO bi-layer films have been investigated and they are compared with the commercially available SnO_2-coated glass substrate. The resistivities of ZnO and SnO₂ films are comparable (10⁻⁴ Ω-cm). Surface morphologies of different transparent conducting oxide coated substrates before and after H-plasma exposure were studied by scanning electron microscopy. The optical transmission of ZnO, SnO₂/ZnO and SnO₂ films are comparable and varies from 85 to 90% in the visible region. The optical transmission reduces drastically to less than 20% in SnO₂ films and for ZnO film it remains almost unchanged after H-plasma exposure. For SnO₂/ZnO film transmission decreases slightly but remains considerably high (80%). The performance of microcrystalline silicon solar cells fabricated on different transparent conducting oxides as substrates (ZnO/glass, SnO₂/glass and ZnO/SnO₂/glass double layer) is investigated in detail.     

Layered GdBa0.5Sr0.5Co2O5+δ as a cathode for intermediate-temperature solid oxide fuel cells

The layered GdBa_0.5Sr_0.5Co₂O_5+δ (GBSC) perovskite oxides are synthesized by Pechini method and investigated as a novel cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The single cell of NiO–SDC (Sm_0.2Ce_0.8O_1.9)/SDC (20 μm)/GBSC (10 μm) is operated from 550 to 700 °C fed with humidified H₂ as fuel and the static air as oxidant. An open circuit voltage of 0.8 V and a maximum power density of 725 mW cm⁻² are achieved at 700 °C. The interfacial polarization resistance is as low as 0.88, 0.29, 0.13 and 0.05 Ω cm² at 550, 600, 650 and 700 °C, respectively. The ratio of polarization resistance to total cell resistance decreases with the increase in the operating temperature, from 60% at 550 °C to 21% at 700 °C, respectively. The experimental results indicate that GBSC is a promising cathode material for IT-SOFCs.     

Photon-assisted synthesis of ultra-thin yttria-doped zirconia membranes: Structure, variable temperature conductivity and micro-fuel cell devices

We report on the synthesis and functional properties of nanoscale (50 nm) dense Y-doped zirconia (YDZ) electrolyte thin films by photon-assisted oxidation of Zr–Y precursor alloy thin films. Crystalline zirconia films with grain size of 5 nm were successfully grown at room temperature by oxidation under ultra-violet (UV) photon irradiation. Microstructure of the films was characterized by transmission electron microscopy. The electrochemical conductivity of UV grown YDZ electrolytes was investigated over a broad range of temperatures using Pt electrodes as a function of yttria doping concentration. The slightly lower electrical conductivity in UV grown films at intermediate temperature range (400–550 °C) is consistent with previous reports on oxygen defect annihilation under photo-excitation. Micro-fuel cells utilizing such ultra-thin YDZ membranes yielded 12 mW cm⁻² power density at 550 °C. The results are of potential relevance in advancing low temperature ultra-thin oxide membrane synthesis for energy applications.     

Investigation of texturization for monocrystalline silicon solar cells with different kinds of alkaline

In this paper, monocrystalline silicon was textured with different kind of etchants for solar cells, respectively. It was found that, only with sodium hydroxide (NaOH) or sodium acetate anhydrous (CH₃COONa) solution, the textural results were very weak, resulting in high reflectance of silicon surface. However, if using the mixture solution of NaOH and CH₃COONa, the reflectance was noticeably decreased. Moreover, the dependence of reflectance on the etching time showed that longer etching time was necessary for texturization in the NaOH+CH₃COONa+H₂O system. And it was also found that the addition of isopropyl alcohol (IPA) to this mixture solution had a detrimental effect on the texturization. All these results suggested that acetate (CH₃COO⁻) plays a similar role as IPA for alkaline texturization, but they cannot coexist. Finally, the mechanisms of texturization with different kinds of etchant were discussed in detail.     

Energy analysis of silicon solar cell modules based on an optical model for arbitrary layers

An optical model for arbitrary layers is developed and a one-dimensional steady-state thermal model is applied to analyze the energy balance of silicon solar cell modules. Experimental measurements show that simulations are in good agreement, with a maximum relative error of 8.43%. The wind speed v_wind, ambient temperature T_amb and irradiance G are three main factors influencing the temperature of a photovoltaic panel. Over the course of a day the electrical output is reduced by the module temperature to only 32.5% of the rated value. Optical studies reveal that before 8:00 hours and after 16:00 hours, significant incident energy is lost by reflection because of the large angle of incidence θ_in, while at other times of day optical losses are nearly the same due to only small changes of transmission for θ_in < 45°. In addition, some optical losses result from the mismatched refractive indexes of encapsulating materials, especially at the ethylene-vinyl-acetate (EVA)/anti-reflection coating (ARC) and the ARC/Si interfaces. The uses of SiO₂ and TiO₂ as ARC materials for un-encapsulated and encapsulated Si solar cells are investigated by simulation. Comparing the results indicates that TiO₂ as ARC reduces the reflective optical loss within λ = 0.4–1.1 μm after encapsulation, while SiO₂ as ARC increases the loss by 5%. Energy allotment analysis shows that from 9:00 to 15:00, the reflective and transmissive optical losses are relatively steady at 26% and 13% of the incident energy, while the convective and radiative heat losses account for a further 30% and 24%, respectively. Thus, only 7% of incident energy is converted to electrical power.     

Thermal imaging of solid oxide fuel cell anode processes

A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H₂ and carbon deposition lead to the fragment cooling by 5 ± 2 °C and 16 ± 1 °C, respectively. When air is flowed over the fragments, the temperature rises 24 ± 1 °C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 ± 0.1 °C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a ΔT of +2.2 ± 0.2 °C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial (0.1 mm) and temperature (0.1 °C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs.